Chemical vapor deposition of iron, ruthenium, and osmium

ABSTRACT

A method is provided for forming films comprising Fe, Ru or Os employing the techniques of chemical vapor deposition to decompose a vapor comprising an organometallic compound of the formula (a): (CO) 4  ML or (b): M 2  [μ-η:η 4  -C 4  ](CO) 6  ; wherein L is a two-electron donor ligand and each R is H, halo, OH, alkyl, perfluoroalkyl or aryl; so as to deposit a coating comprising one or more of said metals on the surface of a substrate.

This invention was made with Government support under Grant No.NSF/ECD-8 721551. The U.S. Government has certain rights in theinvention.

FIELD OF THE INVENTION

This invention relates to chemical vapor deposition of films of thegroup VIII metals, iron, ruthenium, and osmium. The inventionparticularly relates to chemical vapor deposition of ruthenium andosmium and describes new compositions useful in said depositions. Theinvention is also directed to improved chemical vapor deposition methodsfor group VIII metals wherein films of very high quality can be formedat high deposition rates and low temperatures.

BACKGROUND OF THE INVENTION

Vapor Deposition (to be referred to as "CVD" hereinafter) is awidely-used method for depositing a thin film on a substrate. CVD hasbeen extensively described in the literature, including in the patentliterature, and has been comprehensively reviewed by C. E. Morosanu in"Thin Films by Chemical Vapor Deposition", Elsevier, New York (1990).

In CVD, a heat decomposable volatile compound (often an organometalliccompound), which may be called the precursor, is contacted with asubstrate which has been heated to a temperature above the decompositiontemperature of the compound. A coating forms on the substrate which maybe a metal, metal mixture or alloy, ceramic, metal compound or mixturethereof and the like, depending on the choice of precursors and reactionconditions.

The desirable characteristics of CVD as a thin film formation method caninclude its ability to produce a thin film with good step coverage on asubstrate having projections, the ability to readily control thecomposition of the thin film, and the ability to form a thin filmwithout contamination of, or damage to, the substrate.

The deposition of metals from the vapor phase is important in manyindustries, including the electronics industry. In this industry,metallic depositions are often undertaken involving metals such asaluminum, copper, silver, gold, and tungsten. In particular, thesemetals are often used for interconnection lines for semiconductor chips,circuits, and packages. For microelectronic applications, it is oftendesirable to deposit films having high conductivity, which typicallymeans that the films must have minimal carbon and oxygen contamination.

In the electronics and other industries, there is a growing need forvolatile sources of different metals to be used in the CVD of metallicfilms, metal oxide films, metal silicide films, and the like. The keyproperty required for such metal sources is that they readily evaporateor sublime to give a metal-containing vapor or gas, with or without theuse of an additional carrier gas, which vapor or gas can be decomposedin a controlled manner to deposit a film onto a target substrate.

Another use of CVD is to deposit films of metals into vias, trenches,and other recesses or stepped structures. Since it is the situation thatthe deposition must often occur onto substrates which have irregulartopography, a technique is needed to provide conformal deposition, i.e.,deposition of continuous layers over irregular substrates. Whenconformal thin-film deposition is required, techniques such asevaporation and sputtering (which are line-of-sight techniques) cannotbe used. Thus, CVD techniques are highly preferred for this purpose.

While CVD techniques have been described with reference to manytransition metals and to certain other metals (such as copper) andmetalloids (such as silicon), commercial use of CVD for the most parthas been confined to deposition of a few metals and metal compounds,such as silicon, tungsten, and for the co-deposition of certain III-Vand II-VI compounds (denoting, respectively, a compound of a Group IIImetal and a Group V element, and a compound of a Group II metal and aGroup VI element) such as GaAs and ZnSe.

CVD of other metals has not been extensively practiced due to a varietyof reasons including poor film quality, requirement of high processingtemperatures, incorporation of impurities and other defects in thedeposited film, lack of suitable precursor compounds, the inability totransport vapors of the metal complex without decomposition of thevapors, and the instability of the precursors used in the depositionsystems. The availability of suitable volatile and heat decomposablecompounds appears to be the greatest limiting factor in the applicationof CVD to the production of metal containing films.

In addition to the deposition of metal films, formation of transitionmetal oxide coatings on substrates by CVD is known. For example, seeU.S. Pat. Nos. 3,914,515 and 4,927,670 describe depositing transitionmetal oxide films by contacting a cyclopentadienyl metal compounds withheated substrates in the presence of an oxidizing gas.

Chapter III-2 by W. Kern et al., in "Thin Film Processes", J. L. Vossenet al., eds., Academic Press, New York (1978) at pages 258-331 providesa general discussion of CVD of thin films with specific reference tometal oxide films on pages 290-297. Such metal oxide coatings are usefulin photomasks, insulators, semiconductors, high temperaturesuperconductors, and transparent conductors, and as protective coatingsfor high temperature materials.

A CVD method for forming films of refractory metals would overcome someof the problems associated with the use of volatile metals such asaluminum in the manufacture of high density circuitry. Ruthenocene, (C₅H₅)₂ Ru, has been used in the CVD of ruthenium films (D.E. Trent et al.Inorg. Chem., 3, 1057 (1964)), but this precursor has a low volatilityand requires a hydrogen carrier gas to deposit a pure film. U.S. Pat.No. 4,992,305 suggests the use of substituted ruthenocenes and osmocenessuch as bis(isopropylcyclopentadienyl)ruthenium andbis(isopropylcyclopentadienyl)osmium as precursors for ruthenium andosmium CVD, but no examples are given.

Osmium tetrachloride has been used for the CVD of osmium films (S.Lehwald et al., Thin Solid Films, 21, S23 (1974)), but this precursorundergoes considerable decomposition at the temperatures required forits volatilization. Thus much of the precursor is lost in nonproductivereactions. Additionally, high substrate temperatures of about 1250° C.are required for the osmium deposition.

Ruthenium films have been formed by a chemical spray deposition process(J.C. Viguie et al., J. Electrochem. Soc., 122, 585 (1975)).Tris(acetylacetonate)ruthenium in butanol is converted into an aerosolspray using a hydrogen/nitrogen mixture as the carrier gas. Trirutheniumdodecacarbonyl, ruthenocene, and tris(acetylacetonate)ruthenium werecompared as CVD precursors in the formation of ruthenium and rutheniumoxide films by M. Green et al., in J. Electrochem. Soc., 132, 2677(1985). None of these precursors are very volatile and thus highdeposition rates were not attained.

U.S. Pat. No. 4,250,210 discloses the use oftris(acetylacetonate)ruthenium and its fluorinated derivatives in theCVD of ruthenium films. The fluorinated ligands provide greatervolatility and good deposition rates are achieved when the precursor isheated to over 200° C. to assist its volatilization. However,difficulties due to the stabilities of the precursors are noted andfreshly prepared precursors are preferred as aged samples yield inferiorcoatings. Organic byproducts, presumably oligomers of theacetylacetonate ligands, with very low vapor pressures are formed andcollect in the reactor. These liquid deposits represent a seriouscontamination problem in a production scale application of thetris(acetylacetonate)ruthenium precursors. This reference also alludesto the use of ruthenium carbonyl chloride andpenta(trifluorophosphine)ruthenium as precursors for ruthenium CVD.However, these compounds are said to be unsuitable for general usebecause the rates of deposition of ruthenium that can be obtained arevery low. Therefore, these precursors can only be used to deposit verythin coatings which exhibit poor adhesion to substrates. Additionally,ruthenium carbonyl chloride corrodes certain substrates and it isdifficult to obtain a consistent product in its preparation. This lackof consistency in the product can show up as a substantially nonvolatileform of the carbonyl chloride, which decomposes before it canvolatilize.

Although ruthenium thin films have been difficult to prepare, rutheniumand ruthenium oxide have been shown to have utility as electricalcontact materials (R.G. Vadimsky et al., J. Electrochem. Soc., 126, 2017(1979)). Ruthenium oxide and ruthenium metal have similar electricalconductivities and both show good environmental stability. Films ofruthenium and ruthenium oxide deposited by CVD have been proposed to beuseful for contact metallizations, diffusion barriers, and gatemetallizations (M.L. Green et al., J. Electrochem. Soc., 132, 2677(1985)).

Ruthenium oxide electrodes, some prepared by CVD, have shown utility asworking electrodes in nonaqueous solvents (D.R. Rolison et al., J.Electrochem. Soc., 126, 407 (1979)). Thin film multilayercobalt/ruthenium structures, prepared by sputtering techniques, canexhibit novel magnetic properties (S.S.P. Parkin et al., Physical ReviewLetters, 64, 2304 (1990)). In U.S. Pat. No. 4,250,210, CVD films ofruthenium on cutting tools can increase the cutting life of the tool.

CVD of iron using iron pentacarbonyl is well known in the art. Thisprecursor is commercially available and is very volatile. However, itshigh volatility makes iron pentacarbonyl unsuitable for manyapplications, such as its use as a dopant in semiconductor manufacture(J.A. Long et al., J. Crystal Growth, 77, 42 (1986)).

As described by C. E. Morosanu on pages 460-475 in the previously citedbook, iron CVD has shown utility in preparing garnets and ferritesuseful as electronics, microelectronics, microwave electronics,optoelectronics, and the like. Additional utility has been shown in thepreparation of Permalloy (Ni-Fe) magnetic films, photolithographicmasks, and inorganic resists for laser and electron beam lithography.

Thus, a continuing need exists for improved organometallic precursorsuseful for the CVD of films of iron, ruthenium and osmium.

SUMMARY OF THE INVENTION

The present invention provides a method for applying a film comprisingiron, ruthenium or osmium to the surface of a substrate comprisingemploying the techniques of chemical vapor deposition (CVD) to decomposea vapor comprising a compound of formula I:

    (CO).sub.4 ML                                              (I)

or a compound of formula II: ##STR1## on said surface.

M is iron (Fe), ruthenium (Ru) or osmium (Os) in the compound of formula(I) and L is a two-electron donor ligand selected from the groupconsisting of a phosphine ((R¹)₃ P), a phosphite ((R¹ O)₃ P), an amine((R¹)₃ N), an arsine ((R¹)₃ As), a stibene ((R¹)₃ Sb), an ether ((R¹)₂O), a sulfide ((R¹)₂ S), an olefin ((R¹)₂ C═C(R¹)₂), an alkylidene((R¹)₂ C=), an acetylene (R¹ C.tbd.CR¹), a nitrile (R¹ C.tbd.N); anisonitrile (R¹ NC), and a thiocarbonyl (CS), wherein each R¹ is selectedfrom H, halo, alkyl or aryl so that each L has the total number ofcarbon atoms set forth hereinbelow.

In the compound of formula (II), each R is selected from the groupconsisting of H, halo (Cl, F, Br, I), hydroxy, (C₁ -C₁₀)alkyl, (C₁-C₁₀)perfluoralkyl and (C₆ -C₁₀)aryl, or two R groups taken together arebenzo, and each M is Fe, Ru or Os. Preferably, the two M atoms are thesame.

As used herein, with respect to the compounds of formula (I) or formula(II), the term "alkyl" includes branched or straight-chain alkyl,including (C₁ -C₁₉)alkyl, or (C₃ -C₁₀)cycloalkyl wherein, optionally,the carbon chain is interrupted by 1-5, preferably by about 1-2- N,non-peroxide O, S, Si or mixtures thereof, e.g., by NH or SiH₂. As usedherein with respect to the compounds of formula (I) or (II), the term"aryl" includes (C₇ -C₁₀)aralkyl, or (C₇ -C₁₀)alkaryl, preferablyphen(C₁ -C₄)alkyl or (C -C<)alkylphenyl. The term "aryl" also includes(C₅ -C₆)-membered "heteroaryl" wherein 1-3 of the ring carbon atoms havebeen replaced by N, O, S, Si or mixtures thereof. The aryl groups mayalso be substituted by 1-5 moieties such as halogen, preferably by F orCl; (C₁ -C₄)alkoxy, phenoxy or dioxymethylene, or by mixtures thereof

Thus, the present method provides an improved technique for CVD whereincontinuous films comprising the group VIII metals, Fe, Ru, Os, of highquality and good surface morphology can be deposited at lowtemperatures. Preferably, in the absence of an oxygen source, the filmsconsist essentially of Fe, Ru or Os in that they contain only minoramounts of residual element(s) derived from the L groups, the C₄ R₄moiety, or the CO groups, e.g., ≦10% of halogen, carbon, oxygen, etc.Most preferably, the films are essentially pure films of Fe, Ru, or Os.

In another aspect, the present invention provides a CVD method where theabove precursors are used in combination with reactive carrier gases todeposit films of inorganic compounds such as metal oxides. Alternatinglayers of essentially pure metals and of metal oxides wherein the metalsare the same or different, can also be deposited on a single substrate.

Another aspect of this invention provides certain precursor compounds offormulas (I) and (II) which can be used in thermal CVD and radiationbeam induced CVD processes.

Another aspect of this invention provides an improved technique for thedeposition of Fe, Ru, and Os containing films onto substrates ofdifferent shapes, the process providing high quality conformaldeposition onto substrates of irregular topography.

Another aspect of this invention provides an improved thermal andradiation beam induced CVD process for depositing Fe, Ru, and Os, wherethe technique is directly applicable to the manufacture and processingof semiconductor devices and structures, being suitable for applicationssuch as chip metallization and repair of conducting lines.

Another aspect of this invention provides an improved technique forthermal and radiation beam induced CVD of Fe, Ru, and Os where thetemperature used in the deposition can be tailored to be sufficientlylow that these films can be deposited on substrates whose properties aretemperature sensitive, such as on organic polymers.

In yet another aspect, the present invention provides volatile, heatdecomposable compositions comprising compounds of formula II where M isruthenium or osmium and R is trifluoromethyl.

Advantages of the CVD methods of the present invention over the artinclude, but are not limited to:

(a) the high volatility of the precursors of formulas (I) and (II) canobviate the need for inert carrier gases;

(b) the high volatility of the precursors allows for high depositionrates;

(c) the volatility of the precursors can be readily controlled byvarying the ligands (L) and substituent groups (R and R) of theprecursors;

(d) high deposition (substrate) temperatures are not required;

(e) the precursors are generally air stable to the extent that they maybe handled without the protection of inert atmospheres which facilitatesthe loading of precursors into CVD reactors;

(f) the precursors are easily handled in standard CVD apparatus;

(g) the depositions of the films can be radiation beam-induced;

(h) ruthenium films free of carbon contamination are obtained withoutthe need of a reducing atmosphere; and

(i) osmium-containing films can be prepared at low depositiontemperatures and high precursor conversion for the first time.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic representation of a chemical vapor depositionapparatus useful in the practice of the present method.

DETAILED DESCRIPTION OF THE INVENTION A. Organometallic Precursors

In the present invention, organometallic precursors are chosen from

a) a compound of the formula (CO)₄ ML, or

b) a compound of the formula (II), as depicted hereinabove. In accordwith conventional organometallic nomenclature, the general structure offormula II can be abbreviated as M₂ [μ-(η² :η⁴ -C₄ R₄)](CO)₆ or M₂ (C₄R₄)(CO)₆.

The M of formula I represents Fe, Ru, or Os and L represents atwo-electron donor ligand selected from the group consisting of atrivalent amine, phosphine, arsine, and a stibene of the generalformulae (R¹)₃ N, (R¹)₃ P, (R¹)₃ As or (R¹)₃ Sb, respectively, whereineach R¹ is H, halo, alkyl, perfluoroalkyl or aryl, and is selected sothat ligand L contains a total of about 0 to 30 carbon atoms; phosphites((R¹ O)₃ P), wherein each R¹ is alkyl, perfluoroalkyl or aryl and isselected so that the phosphite contains 3 to 30 carbon atoms; a divalentether (R¹ OR¹), a divalent sulfide (R¹ SR¹), a nitrile (R¹ CN), or anisonitrile (R¹ NC), wherein each R¹ is alkyl, perfluoroalkyl, or aryland is selected so that the ether, sulfide, nitrile, or isonitrilecontains 2-30 carbon atoms; an olefin ((R¹)₂ C═C(R¹)₂, or an acetylene(R¹ C.tbd.CR¹), wherein each R¹ is H, halo, alkyl, perfluoroalkyl,--CHO, --CN, (tri(C₁ -C₄)alkyl)silyl or aryl, and is selected so thatthe olefin or acetylene has 2-30 carbon atoms; thiocarbonyl (CS), oralkylidene ((R¹)₂ C═), wherein each R¹ is H, alkyl, perfluoroalkyl,halo, amino or aryl and is selected so that the alkylidene has 1 to 30carbon atoms.

Preferably, alkyl, perfluoroalkyl and aryl in group L, are as definedhereinabove for alkyl, perfluoroalkyl and aryl in the compound offormula (II). Alkylidene also includes (C₅ -C₁₀)cycloalkylidene and 5-and 6-membered heterocycloalkylidene, wherein the ring comprises 1-4 N,S, Si, non-peroxide O or mixtures thereof. Preferred R¹ groups include,but are not limited to, halo, (C₁ -C₄)alkyl, (C₁ -C₄)perfluoroalkyl,phenyl, H, CHO and mixtures thereof.

R in formula (II) preferably is hydrogen, OH, halo, (C₁ -C₆)alkyl, (C₁-C₆)perfluoroalkyl, and phenyl, most preferably trifluoromethyl, phenylor methyl. The four R groups need not be all identical and the two Mgroups need not be identical.

The ligands of formula I are generally known to those skilled in the artand are described by J. P. Collman and L. S. Hegedus in "Principles andApplications of Organotransition Metal Chemistry" University ScienceBooks, Mill Valley, Calif. (1980) at pages 51-175.

Useful precursors of formula I wherein L is an acetylenic ligand includethose in which L is hexafluoro-2-butyne, such as(hexafluoro-2-butyne)rutheniumtetracarbonyl, hereinafter abbreviatedRu(hfb)(CO)₄. This precursor has been successfully used to depositanalytically pure ruthenium coatings at temperatures between about 300and 600° C.

A preferred precursor of formula II which is useful for the depositionof ruthenium is Ru₂ {μ-[η² :η⁴ -C₄ (CF₃)₄ ]}(CO)₆, hereinafterabbreviated Ru₂ [C₄ (CF₃)₄ ](CO)₆. This precursor has also beensuccessfully used to deposit analytically pure ruthenium coatings attemperatures between about 300° and 600° C.

The synthesis of a series of monometallic alkyne tetracarbonyl complexesof group VIII metals has been reported by R.G. Ball et al., J.Organometallics, 6, 1918 (1987). When the alkyne is hexafluoro-2-butyne(hfb), the ruthenium and osmium complexes M(hfb)(CO)₄ can be prepared ingood yield (M.R. Gagne et al., J. Organometallics, 7, 561 (1988)). Ageneral method for the synthesis of M(hfb)(CO)₄ complexes comprises thephotolysis of M(CO)₅ in the presence of the hfb ligand. The presence oftrifluoromethyl groups enhances the volatility of the complexes comparedto nonfluorinated analogs. The Ru(hfb)(CO)₄ compound has a vaporpressure between 1 and 2 torr at room temperature and thus is suitablefor CVD experiments.

Heating the M(hfb)(CO)₄ complexes where M is Ru or Os at temperaturesfrom about 100° C. to about 300° C. results in the formation of thenovel dinuclear complexes M₂ [C₄ (CF₃)₄ ](CO)₆. The reactions proceed ingood yield in solution or in the gas phase and formally involve thedimerization of the hfb ligands. These dimetallic complexes, despitetheir crystallinity and high molecular weights, sublime under vacuum andare thus suitable for CVD experiments.

Complexes of formula I where M is iron and L is phosphine, amine,phosphite, and the like are generally prepared by reaction of ironpentacarbonyl, diiron nonacarbonyl, or triiron dodecacarbonyl with thedesired ligand L under the influence of heat or light as described byD.F. Shriver et al., "Iron Compounds without Hydrocarbon Ligands",Chapter 31.1 in Comprehensive Organometallic Chemistry, Vol. 4, G.Wilkinson et al., eds., Pergamon Press, Oxford, (1982) at pages 243-329(hereinafter cited as Comp. Organometal. Chem.). Typical methods forsynthesis of (CO)₄ FeL complexes where L is carbene or alkylidene aredescribed by M.D. Johnson "Mononuclear Iron Compounds with η¹-Hydrocarbon Ligands", Chapter 31.2 in Comp. Organometal. Chem., atpages 331-376, and include conversion of a carbonyl ligand into acarbene ligand, reaction of iron pentacarbonyl with electron richolefins, and reaction of iron carbonyl anions with organic cations.

Typical methods for synthesis of (CO)₄ FeL complexes where L is alkeneand alkyne are described by A.J. Deeming in Chapter 31.3 in Comp.Organometal. Chem., at pages 377-512, and include reaction of diironnonacarbonyl or triiron dodecacarbonyl with an alkene, photolysis ofiron pentacarbonyl in the presence of an alkene or alkyne, nucleophilicaddition to the allyl ligand of Fe(CO)₄ (allyl)⁺, and reaction ofalkynes with FeH(CO)₄ ⁻ followed by protonation.

When M is ruthenium, complexes of formula I may be prepared by thermalor photolytic reaction of ruthenium pentacarbonyl or trirutheniumdodecacarbonyl with ligands such as phosphines as described by M.A.Bennett et al., in Chapter 32.3 of Comp. Organometal. Chem., at pages691-820. Displacement of olefin from (CO)₄ Ru(olefin) complexes byligands such as trimethyl phosphite is another general route to (CO)₄RuL complexes (F.-W. Grevels et al. J. Am. Chem. Soc., 103, 4069(1981)).

When M is osmium, complexes of formula I may be prepared by thermalreaction of cis-Os(CO)₄ (H)CH₃ with ligands such as ethylene andtriethylphosphine as disclosed by W.J. Carter et al., in Inorg. Chem.,21, 3955 (1982) or by photolysis of triosmium dodecacarbonyl in thepresence of ligand (R.G. Ball et al., J. Organometallics, 6, 1918(1987)). Reactions of Os(CO)₄ ⁻² with thiazolium salts lead to (CO)₄ OsLcomplexes where L is a carbene ligand (M. Green et al., J. Chem. Soc.,Dalton Trans., 939 (1975)).

Complexes of formula II where M is iron may be prepared by the thermalreaction of acetylenic compounds with iron pentacarbonyl, Fe(CO)₃ (η⁴-benzalacetone), diiron nonacarbonyl, or triiron dodecacarbonyl asdescribed by W.P. Fehlhammer et al., Chapter 31.4 in Comp. Organometal.Chem., at pages 513-613. The corresponding ruthenium analogs areprepared by reaction of triruthenium dodecacarbonyl with alkynes orbutadienes as described by M.A. Bennett et al. Chapter 32.4 in Comp.Organometal. Chem., at pages 821-841. The corresponding osmium analogsare prepared by reaction of Os₃ (H)₂ (CO)₁₀ or Os₃ (CO)₁₂ withacetylenes or dienes as described by R.D. Adams et al., Chapter 33 inComp. Organometal. Chem., at pages 967-1064.

The precursor complexes of formula I and formula II may vary in theirair and thermal stability depending on the ligands and substituentgroups incorporated into the complexes. The air stability of complexesof formula I and II are generally quite good allowing the complexes tobe handled without the need to employ inert atmospheres such as nitrogenor argon. This is important in commercial application of theseprecursors as the need for inert atmosphere increases the operatingcosts and capital equipment costs for any CVD process.

The ability to easily vary the ligand L of complexes of formula I andthe R groups of complexes of formula II provides an exceptional degreeof control over both the volatility and deposition temperature for theprecursors of the present invention. For example, Fe(CO)₄ [P(C₆ H₅)₃ ]melts at about 201° C. and sublimes at about 100° C. which makes itdistinctly less volatile than Fe(CO)₄ [P(OCH₃)₃ ] which melts at about45° C. and sublimes at room temperature. The choice of ligands informula I and substituent groups in formula II has an effect on theelectron density at the metal centers of these complexes. This in turneffects the thermal stability of the precursor complexes whichdetermines the deposition temperature for a given precursor complex. Theability to control both the deposition rate (through precursorvolatility) and the deposition temperature (through precursor stability)with one variable, L or R, greatly facilitates precursor design for theCVD of iron, ruthenium, and osmium.

Illustrative examples of precursor complexes of formula I includetetracarbonyl(trichlorophosphine)iron,tetracarbonyl(trifluorophosphine)iron, tetracarbonyl(phosphine)iron,tetracarbonyl(thiocarbonyl)iron, tetracarbonyl(diaminomethylene)iron,tetracarbonyl(tetrafluoroethylene)iron,tetracarbonyl(chloroethylene)iron, tetracarbonyl(isocyanomethane)iron,tetracarbonyl(ethylene)iron, tetracarbonyl(cyanoethylene)iron,tetracarbonyl(acrolein)iron,tetracarbonyl(1,4-dimethyltetrazolin-5-ylidene)iron,tetracarbonyl(trimethylarsine)iron,tetracarbonyl(trimethylphosphine)iron,tetracarbonyl(trimethylstibine)iron, tetracarbonyl(trimethylamine)iron,tetracarbonyl(trimethylphosphite)iron, tetracarbonyl(1,3-dithiane)iron,tetracarbonyl(1,3-dimethyl- 2-imidazolidinylidene)iron,tetracarbonyl(isocyanobenzene)iron, tetracarbonyl(styrene)iron,tetracarbonyl(di-t-butylacetylene)iron,tetracarbonyl[bis(trimethylsilyl)ethyne]iron,tetracarbonyl(triphenylarsine)iron,tetracarbonyl(triphenylphosphine)iron,tetracarbonyl(triphenylstibine)iron,tetracarbonyl(triphenylphosphite)iron,tetracarbonyl(trifluorophoshine)ruthenium,tetracarbonyl(acrylonitrile)ruthenium,tetracarbonyl(triphenylphosphine)ruthenium,tetracarbonyl(trimethylphosphite)ruthenium,tetracarbonyl(trimethylphosphine)ruthenium,tetracarbonyl[3,4-dimethyl-2(3H)-thiazolylidene]osmium,tetracarbonyl(ethylene)osmium,tetracarbonyl[bis(trimethylsilyl)ethyne]osmium,tetracarbonyl(trimethylphosphite)osmium,tetracarbonyl(trifluorophoshine)osmium,tetracarbonyl(triethylphosphine)osmium, andtetracarbonyl(triphenylphosphine)osmium.

Illustrative examples of precursor complexes of formula II includehexacarbonyl[μ-(η² :η⁴-(3,5-cyclohexadiene-1,2-diylidenedimethylidyne)]diiron,hexacarbonyl[μ-(η² :η⁴ -1,2-ethenediyl-1,2-phenylene]diiron,hexacarbonyl[μ-(η² :η⁴-1,2,3,4-tetramethyl-1,3-butadiene-1,4diyl)]diiron, hexacarbonyl[μ-(η²:η⁴ -1,3-butadiene-1,4diyl)]diiron, hexacarbonyl[μ-(η² :η⁴-1,4-dihydroxy-1,3-butadiene-1,4-diyl)]diiron, hexacarbonyl[μ-(η² :η⁴-1,2-ethenediyl-1,2-phenylene)]diruthenium, hexacarbonyl[μ-(η² :η⁴-1,2,3,4-tetramethyl1,3-butadiene-1,4-diyl)]diruthenium,hexacarbonyl[μ-(η² :η⁴-1,2,3,4-tetraphenyl-1,3-butadiene-1,4-diyl)]diruthenium,tricarbonyl[μ-(η² :η⁴-1,2,3,4-tetraphenyl-1,3-butadiene-1,4diyl)](tricarbonyliron)ruthenium,hexacarbonyl[μ-(η² :η⁴ -1,3-butadiene-1,4-diyl)]diosmium,hexacarbonyl[μ-(η² :η⁴-1,2,3,4-tetramethyl-1,3-butadiene-1,4-diyl)]diosmium, andhexacarbonyl[μ-(η² :η⁴ -1,2-ethenediyl-1,2-phenylene)]diosmium.

B. Substrates

Any type of substrate can be used, including metals, graphite,semiconductors, insulators, ceramics and the like as long as thesubstrate is not substantially deteriorated under the depositionconditions Such substrates include, but are not limited to, silicon, tinoxide, gallium arsenide (GaAs), silica, glass, alumina, zirconia, aswell as polyimide, polymethyl-methacrylate, polystyrene and othersynthetic polymers More specifically, substrates useful for electronicdevice applications include Si<100>, Si<311>, Si<111>, Si<110>,GaAs<110>, GaAs<111> and GaAs<311>.

Although the exemplified substrate surfaces are planar, the presentprocess can provide conformal deposition so that the metals can bedeposited as continuous layers into recesses, trenches, and vias, andover stepped surfaces, such as those which are topologicallymicrostructured. The substrate can be of any desired shape, eitherregular or irregular. Thus, the substrate can be a rectangular solid orother solid characterized by flat exterior surfaces. Cylindricalsurfaces, such as rods and wires, can also be coated according to thisinvention. Spherical surfaces and other curved surfaces can also becoated. The substrate can even be particulate and/or be hollow, as forexample, a tube or a hollow or porous sphere or irregular particlehaving openings to the exterior.

C. Chemical Vapor Deposition

This invention broadly relates to the use of the technique of CVD todeposit high quality metal-containing films of group VIII metals, andspecifically films of Ru and Os, at low temperature on a wide variety ofsubstrates. As described by C.E. Morosanu in "Thin Films by ChemicalVapor Deposition,"Elsevier, N.Y. (1990) at pages 42-54, CVD isclassified into various types in accordance with the heating method, gaspressure, and/or chemical reaction. For example, conventional CVDmethods include (a) cold wall type CVD, in which only a depositionsubstrate is heated; (b) hot wall type CVD, in which an entire reactionchamber is heated; (c) atmospheric CVD, in which reaction occurs at apressure of about one atmosphere; (d) low-pressure CVD in which reactionoccurs at pressures from about 10⁻¹ to 100 torr; (e) electron-beamassisted CVD and ion-beam assisted CVD in which the energy from anelectron-beam or an ion-beam directed towards the substrate provides theenergy for decomposition of the precursor; (f) plasma assisted CVD andphoto-assisted CVD in which the energy from a plasma or a light sourceactivates the precursor to allow depositions at reduced substratetemperatures; and (g) laser assisted CVD wherein laser light is used toheat the substrate or to effect photolytic reactions in the precursorgas.

The laser CVD method is thoroughly discussed by I.P. Herman, ChemicalReviews, 89, 1323 (1989). Pyrolytic depositions are discussed on pages1346-8 and photolytic depositions are discussed on pages 1348-9 of thisreview. An example of ion-beam assisted CVD is found in U.S. Pat. No.4,876,112. An example of photo-assisted CVD is found in U.S. Pat. No.5,005,519. An example of laser assisted CVD is found in U.S. Pat. No.4,340,617. An example of electron-beam assisted CVD is found in U.S.Pat. No. 4,713,258. An example of plasma assisted CVD is found in U.S.Pat. No. 4,721,631. Examples of low pressure CVD and hot wall CVD arefound in U.S. Pat. No. 4,923,717. An example of atmospheric CVD is foundin U.S. Pat. No. 5,022,905. Examples of low pressure CVD and cold wallCVD are found in U.S. Pat. No. 4,868,005. Heating of substrates in acold wall CVD reactor may be accomplished by several methods includingthe use of hot stages or induction heating.

Broadly, thermal CVD includes any type of apparatus in which thesubstrate and/or the gaseous precursor is heated and could includestandard thermal reactors such as cold wall/hot substrate reactors andhot wall type reactors, as well as radiation beam reactors in which abeam (such as a laser beam) is used to heat the substrate and/or todecompose gaseous precursor.

D. The CVD Process

In a typical CVD process, the substrate on which deposition is to occuris placed in a reaction chamber, and is heated to a temperaturesufficient to cause the decomposition of vapors of the precursorcomplex. When these vapors are introduced into the reaction chamber andtransported to the vicinity of the substrate, they will decomposethereon to deposit a film containing the group VIII metal. It isbelieved that the decomposition includes the initial dissociation of acarbonyl ligand, followed by sequential or concerted loss of theremaining ligands.

In a thermal reactor CVD system, it is preferable that the decompositionreaction occur at the substrate, and for this reason it is preferable toheat the substrate to a temperature in excess of the decompositiontemperature of the precursor complex. In a radiation beam induced CVDtechnique, the radiation (such as an ion beam) is preferably used toheat the substrate so that decomposition of the precursor occurs at thesubstrate.

These CVD processes can be used to provide blanket deposition of Fe, Ru,and Os on substrates, as well as to provide deposition of these metalson selected areas of the substrate, i.e., by use of a masking material,such as a resist material. Additionally, selected area depositions maybe accomplished by energy beam assisted CVD where a beam of energy, suchas an ion beam, selectively heats small portions of the substrate.

Any CVD apparatus design may be used in the present invention includinghot wall reactors, cold wall reactors, radiation beam assisted reactors,plasma assisted reactors, and the like. For blanket depositions, a coldwall-hot substrate reactor may sometimes be preferred as this design isefficient in regards to precursor consumption. For selected areadepositions, a radiation beam assisted reactor may be preferred as theradiation beam may be used to "write" metal containing films onto smallareas of the substrate.

As embodied herein, the growth of Fe, Ru and Os films is conductedwithout a carrier gas, and under a dynamic vacuum of about 1-10 mtorr ina standard hot-wall, horizontal tube CVD reactor. Such a reactor (2),adapted for low pressure CVD, is schematically depicted in FIG. 1.

As shown in FIG. 1, the precursor is contained in a reservoir (1), atone end of the reactor (2), is exposed to a vacuum by opening valve (3)and vaporized for a sufficient time to produce a surface coating (9) ofFe, Os or Ru on substrate (6). The vacuum can be provided by a suitablevacuum pump positioned at the opposite end of reaction chamber (5) (notshown). The precursor vapor (8) then passes into a reaction chamber (5)that contains one or more units of the substrate (6). The substrate,e.g., wafers of Si<100>, are preferably held in a vertical position by asuitable holder (7). The reaction chamber is maintained at a preselectedtemperature, by means of an external furnace (10), which is effective todecompose the precursor vapor (8) so as to deposit a film of Os, Ru orFe (9) on the exposed surfaces of the substrate units. Preferably, thereaction chamber is maintained at about 150°-700° C. during thedeposition process, most preferably at about 300°-600° C.

Generally, vacuum systems are used for CVD of these metals. There is nocriticality with respect to the pressure in the system, operatingpressures of 1 to 100 mtorr have been used in the absence of carrier gasand higher or lower pressures are also acceptable, i.e., up to about 2torr. These pressures are largely determined by the pumping speed of thevacuum equipment, the vapor pressure of the precursor complex, and inertcarrier gasses can be added to increase the total pressure.

Although it is preferred to conduct the present process without acarrier gas, it is often desirable to use a carrier gas in a CVDprocess, which is passed through or over a solid or liquid precursor.This is especially true when a metal compound deposition rather than apure metal deposition is required. In this case, a reactive carrier gassuch as an oxygen-containing carrier gas (air, oxygen or nitrous oxide),or ammonia, silane, hydrogen sulfide, and the like or combination ofinert and reactive carrier gases may be used. When carrier gases areused pressures may range from about 0.1 torr to about 760 torr(atmospheric pressure) and are more typically in the range of 20 to 300torr. However, this pressure does not appear to be highly critical tothe deposition of the films.

The precursor is generally maintained at a constant temperature duringthe vaporization process for ease of handling; however, this is notcritical. The temperature is generally below the respectivedecomposition temperature, but at a temperature such that it issufficiently capable of being volatilized in the process of chemicalvapor deposition.

Prior to initiating CVD, the substrates, such as Si<100> wafers, arepre-cleaned by the standard means of sequential soaking in baths oftetrachloroethane, methanol, distilled water, dilute hydrofluoric acid,and distilled water. The wafers are placed at several locations towardsthe entrance to the reactor tube, where there is a steep rise intemperature. At 500° C. exposure of the wafers to the vapors ofRu(hfb)(CO)₄ for three minutes, produces a film having a thickness of1800Å as determined by stylus profilometry. The films are smooth andhighly reflective to visual inspection and have a color nearly identicalto that of the silicon substrate.

When the temperature of the deposition is lowered to 300° C., the rateof film deposition is decreased and a yellow crystalline solid isobserved condensing on the walls of the cooler portions of the reactor.This solid was determined to be a new compound, which was completelycharacterized using analytical and spectroscopic methods and wasdetermined to be Ru₂ [C₄ (CF₃)₄ ](CO)₆. This compound results from lossof CO and coupling of the alkyne ligands from two equivalents ofRu(hfb)(CO)₄.

Within the iron triad, numerous examples of this structural type areknown. See, A.N. Nesmeyanov et al., J. Organomet. Chem., 47, 1 (1973).The dimetallic Ru₂ [C₄ (CF₃)₄ ](CO)₆ complex can also be synthesized byheating a toluene solution of Ru(hfb)(CO)₄ at reflux for 3 hr. Theobservation that this chemistry occurs equally well both in toluenesolution (where surface effects should be minimized) and in the vacuumpyrolysis suggests that the initial chemistry in the CVD process takesplace in the gas phase as shown in the following equation.

    Ru(hfb)(CO).sub.4 → Ru(hfb)(CO).sub.3 +CO

At temperatures where Ru(hfb)(CO)₃ has a long enough lifetime to collidewith another complex, presumably Ru(hfb)(CO)₄, formation of thedinuclear complex may be favored as shown in the following equation.

    Ru(hfb)(CO).sub.3 +Ru(hfb)(CO).sub.4 → Ru.sub.2 [C.sub.4 (CF.sub.3).sub.4 ](CO).sub.6 +CO

At higher temperatures further ligand loss from Ru(hfb)(CO)₃ ispredominant leading to metallic films of ruthenium as shown in thefollowing equation.

    Ru(hfb)(CO).sub.3 → Ru+hfb+3 CO

Similar chemistry is believed to occur for the iron and osmium analogs.

With Os(hfb)(CO)₄, slightly higher deposition temperature and slightlylonger deposition times are required than those used with Ru(hfb)(CO)₄.For example, at 600° C., a 1500Å thick film of osmium is formed in tenminutes.

Smooth, reflective iron films which adhere well to Si<100> substratesare also produced by the present invention. Both Fe(CO)₄ [N(CH₃)₃ ] andFe(CO)₄ [P(OCH₃)₃ ] yield iron films which contain varying amounts ofcarbon and oxygen as determined by Auger electron spectroscopy. Thedepositions are carried out at temperatures from 150° to 500° C. Traceamounts of nitrogen are detected in films deposited from Fe(CO)₄[N(CH₃)₃ ] at low temperatures and phosphorous is r present in filmsdeposited from Fe(CO)₄ [P(OCH₃)₃ ]. Thus, the molecular composition ofprecursors may be used as a means of introducing other elements into thedeposited metal films.

Although its volatility is significantly less than Ru(hfb)(CO)₄,ruthenium films can be prepared at 600° C. using Ru₂ [C₄ (CF₃)₄ ](CO)₆.A ten-minute deposition gives reflective, smooth, adherent rutheniumfilms on Si<100> substrates. These films contain no detectable carbonand only traces of oxygen and fluorine. Depositions from Os₂ [C₄ (CF₃)₄](CO)₆ can provide osmium films in an analogous manner.

The readily available iron compounds of formula II are also effectiveprecursors to iron films. The crystalline Fe₂ (C₄ H₄)(CO)₆ compound isair stable and easily handled by standard techniques. The compound alsosublimes easily and is thus suitable for CVD studies. At 500° C., Fe₂(C₄ H₄)(CO)₆ rapidily deposits smooth, adherent films containing iron onsilicon substrates. Deposition from the precursors of formula II is alsobelieved to involve initial loss of a carbonyl ligand followed bysequential or concerted loss of the remaining ligands. The precursors offormula II contain a metal-to-metal bond which may remain intact duringthe deposition sequence.

Although the precursor complexes M(hfb)(CO)₄ and M₂ [C₄ (CF₃)₄ ](CO)₆contain relatively high levels of fluorine in their atomic composition,metallic films deposited from these materials contain undetectable oronly trace amounts of fluorine as determined Auger electronspectroscopy.

Trapping the volatile byproducts from a Ru(hfb)(CO)₄ CVD experiment isaccomplished using a liquid nitrogen cooled U-tube filled with glassbeads. The trapped products are distilled into a NMR tube which issealed under vacuum. After obtaining a ¹⁹ F NMR spectrum, the contentsof the tube are further analyzed using GC-MS-FTIR. These methodsestablish that the majority of the material is hexafluoro-2-butyne.Thus, the hfb ligand can be readily trapped for reuse in the presentmethod. The gas chromatogram also shows the elution of two smaller, lesswell-resolved peaks immediately following the elution of hfb. Thehighest mass values for these two peaks are m./e =362 and 324,respectively. These values and the associated fragmentation patternscorrespond to the formulas C₈ F₁₄ and C₈ F₁₂ which may result fromdecomposition of Ru₂ [C₄ (CF₃)₄ ](CO)₆.

Metal oxide coatings can be formed by using as precursor a compound offormula I or II which yields the desired metal on decomposition. Theprecursor is contacted with a heated substrate in the presence of anoxidizing agent, which is preferably a mildly oxidizing gaseous oxygensource. The oxidizing agent may also be any gaseous reactant which iscapable of reacting with the organometallic precursor compounds at thedecomposition temperatures of the latter to form metal oxide deposits.Oxygen-containing compounds, such as nitrous oxide, carbon dioxide, THF(tetrahydrofuran) and steam can be used in some cases, in place ofoxygen or air for the deposition of metal oxides and oxygen-containingsalts since the oxygen compounds react with the organometallicprecursors only at high temperatures. The oxidizing agent may beintroduced into the reactor in admixture with a carrier gas. Forexample, nitrous oxide/nitrogen oxidizing mixtures are suitable.

Group VIII metal oxide films are produced by the present method.Deposition from Ru(hfb)(CO)₄ give adherent, metallic ruthenium oxidefilms on Si<100> substrates when the depositions are carried out inoxidizing atmospheres of air or oxygen. Auger electron spectroscopyshows the concentration of oxygen to be constant throughout the depth ofthe film demonstrating that the oxygen is incorporated from thedeposition atmosphere and does not merely result from post depositionexposure of the films to air. Quantification of the ruthenium, oxygen,and carbon levels in the ruthenium oxide films is difficult, sinceoxygen affects the ruthenium signals in the Auger electron spectrum(M.L. Green et al., J. Electrochem. Soc., 132, 2677 (1985)).

Alloys, metal mixtures and intermetallic compounds can also be depositedin accordance with this invention, by contacting one or more precursorcompounds of formula I or II and one or more additional heatdecomposable precursor compounds which yield the desired additionalmetals or metalloids on decomposition. Preferably, the deposition iscarried out under nonoxidizing or reducing conditions. An example of anadditional heat decomposable precursor is diethylselenide. The term,"metalloid", as used herein refers to a solid nonmetallic element andincludes arsenic, antimony, boron, germanium, phosphorus, selenium,silicon, sulfur, and tellurium.

As will be seen from the examples to follow, high quality metal filmscan be deposited with thicknesses dependent upon the time andtemperature of deposition. Products of this invention may have anydesired coating thickness ranging from monomolecular up to about onemillimeter. A preferred range of thickness is from about 0.01 to about100 microns, especially from about 0.1 to about 20 microns. Films havinga thickness of about 0.1 microns and more are most suitable for devicepurposes.

Coating thickness can also be controlled by controlling the flow rate ofthe vapor of the organometallic precursor, the volatility of theorganometallic precursor, and the length of time over which thesecompounds are contacted with substrate.

Products of this invention may be characterized as composite articleshaving a metal containing coating thereon. Single layer coatings,usually of substantially uniform composition throughout, can be achievedwith any of the processes described herein. Precursors of the presentinvention are also useful in molecular beam epitaxy (MBE) and chemicalbeam epitaxy (CBE) processes. In these processes, multilayer structuresof well defined composition and sharp interfacial boundaries aretypically produced. Multiple layer coatings having differentcompositions are best achieved with MBE or CBE. The electricalconductivity of thin films generally increases as the thicknessincreases due to the reduction of electron scattering in the grainboundaries, which is a property of the metals.

Metals and metal compounds deposited by the present invention also haveutility as abrasion resistant coatings for cutting tools and the like,as interconnection traces for microelectronic devices, as corrosionresistant coatings, as magnetic coatings, as contact metallizations, aselectrode materials, as semiconductor dopants, and the like. The CVDprecursors of the present invention have additional utility in therelated process of chemical vapor infusion, typically referred to asCVI, in which a volatile, decomposable material infuses into and ontoporous substrates where they are decomposed. See T.M. Besmann et al.,Science, 253, 1104 (1991). Material thus treated is useful as, forexample, continuous-filament ceramic composites and heterogeneouscatalysts.

The invention will be further illustrated by the following detailedexamples, but the particular materials and amounts thereof recited inthese examples, as well as other conditions and details should not beconstrued to unduly limit this invention.

EXAMPLE 1

Ru(hfb)(CO)₄ was prepared by the method of M.R. Gagne et al., J.Organometallics, 7, 561 (1988), and 0.25 g was placed in a glass flaskthat was fitted with a capacitance manometer and a side armincorporating a stopcock to allow the flask to be attached to a vacuumline. The manometer fitting also incorporated a stopcock to allow themanometer to be isolated from the rest of the system. The flask wassealed, attached to a vacuum line, and cooled to -196° C. by externalapplication of a liquid nitrogen bath. The entire flask was evacuated to1 mtorr while maintaining the -196° C. temperature. The stopcocksleading to the manometer and vacuum line were closed and the flaskallowed to warm to 25° C. The stopcock leading to the manometer was thenopened and the pressure due to the vaporizing Ru(hfb)(CO)₄ monitored for20 minutes. This procedure was repeated three times and the averagevalue for the vapor pressure of Ru(hfb)(CO)₄ at 25° C. was 1.5 torr.This example shows Ru(hfb)(CO)₄ is of a suitable volatility for CVDprocesses and that the material may be handled in standard glass vacuumapparatus.

EXAMPLE 2

The reactor employed in the low pressure chemical vapor deposition of Ruwas a standard hot-wall quartz reactor system (2) equipped with aprecursor pot, a rotary vane oil vacuum pump, vacuum trap, and tubefurnace and was similar to that described in U.S. Pat. No. 4,923,717,and depicted in FIG. 1. The quartz reactor tube (5) had an insidediameter of 2.6 cm and a length of 35 cm. The temperature of the reactorwas monitored by a thermocouple placed between the furnace heatingelements (10) and the outside wall of the quartz reactor tube (5) at aposition directly below the location of the substrates (6). Thesubstrates (6) were placed in a vertical holder (7) between 1 to 5 cmfrom the edge of the furnace. The Si<100> substrates (Mycosil Company,Milpitas, Calif.) were degreased and etched by sequential immersion inthe following baths for 10 min each: tetrachloroethane, methanol,distilled water, dilute hydrofluoric acid, and distilled water. Thesubstrates were placed in the reactor tube, and the system evacuated toapproximately 1 mtorr. The substrates were heated to the depositiontemperature (500° C.) for 30 minutes prior to beginning the deposition.The valve (3) to the reservoir (1) containing Ru(hfb)(CO)₄ (4) wasopened for 3 min to bring Ru(hfb)(CO)₄ vapor (8) into contact with thesubstrate wafers (6). A highly reflective, smooth, adherent coating ofmetallic Ru (9) was formed on the substrate. This example shows thatRu(hfb)(CO)₄ is an effective CVD precursor for ruthenium-containingfilms, that standard CVD equipment may be used, and that carrier gasesand ultra-high temperatures are not required.

EXAMPLE 3

The CVD apparatus described in Example 2 was equipped with a liquidnitrogen cooled, glass bead filled U-tube trap located down stream ofthe reactor furnace. The U-tube trap incorporated a side arm with aground glass joint and a stopcock to allow sampling of the trappedmaterial. The U-tube trap also incorporated stopcocks which allow thetrap to be removed from the CVD reactor system without exposing thecontents to ambient atmosphere. A deposition using Ru(hfb)(CO)₄ wascarried out as described in Example 2 to yield ruthenium metal films.The U-tube trap was removed from the system and the trapped volatileproducts distilled into an NMR tube containing benzene-d₆. The ¹⁹ F NMRspectrum of this material contained one major peak at -53.2 ppm relativeto CFCl₃. A portion of the material from the NMR tube was analyzed byGC-MS-FTIR and the major component had a molecular ion peak at a mass of162 and C-F stretching bands at 1183-1286 cm⁻¹. An authentic sample ofhexafluoro-2-butyne (PCR Incorporated, Gainesville, Fla.) had identical¹⁹ F NMR, MS, and IR spectra to the major component of the above trappedvolatiles. This example shows that the major volatile byproduct from CVDwith Ru(hfb)(CO)₄ is hexafluoro-2-butyne and that the free ligand isreadily trapped for reuse in the synthesis of Ru(hfb)(CO)₄ andsubsequent film depositions.

EXAMPLE 4

Deposition from Ru(hfb)(CO)₄ was carried out as in Example 2 except thatportions of the silicon substrates were masked by placing a small pieceof silicon directly in front of the substrate such that a corner of thesubstrate is covered, as shown in FIG. 1 as (11). The resultingruthenium films had sharp boundaries suitable for thickness measurementsby stylus profilometry. A film thickness of 1800Å was observed for athree-minute deposition at 500° C. which gives a deposition rate of 60nm/min.

EXAMPLE 5

Deposition from Ru(hfb)(CO)₄ was carried out as in Example 2 and theresulting ruthenium films were analyzed by Auger electron spectroscopy(AES). The films were Ar⁺ sputtered for 5 minutes to remove surfacecontaminants resulting from atmospheric exposure. The Auger spectrumshowed a 1% oxygen content of the film. Direct measurement of the carboncontent was not possible by AES due to the overlap between the carbonKLL line at 271 eV and the ruthenium MNN line at 273 ev. The ratio ofthe intensities of the ruthenium transitions located at 273 and 231 eVmay be used as a gauge of the carbon content in ruthenium thin films(M.L. Green et al., J. Electrochem. Soc., 132, 2677 (1985)). In a bulkruthenium, the I₂₇₃ /I₂₃₁ ratio is 2.64. In the films of this examplegrown from Ru(hfb)(CO)₄, the I₂₇₃ /I₂₃₁ ratio is also 2.64. Thisindicates that the carbon content is below the limits of detection. Nofluorine lines is observed in the AES of the CVD films of this example.This example shows the ruthenium films prepared by CVD from Ru(hfb)(CO)₄are of high purity.

EXAMPLE 6

Deposition from Ru(hfb)(CO)₄ was carried out as in Example 2 and theresulting ruthenium films analyzed by X-ray diffraction (XRD), scanningelectron microscopy (SEM), and resistivity measurements. XRD showed thatthe films have a hexagonal structure and are polycrystalline with nopreferential orientation. SEM of the surface of the visually smooth,mirror-like films revealed a grainy morphology with individual grainsizes of approximately 30 nm or less. The resistivity of the films wasmeasured by a standard four-point probe method and yielded a value of160 μΩ/cm. The value for the resistivity of bulk ruthenium is 7.6 μΩ/cm.

EXAMPLE 7

Using the reactor system described in Example 2, osmium thin films weredeposited on Si<100> wafers from Os(hfb)(CO)₄ which was synthesized asdisclosed by M.R. Gagne et al., J. Organometallics, 7, 561 (1988). Thedeposition was performed without a carrier gas under a dynamic vacuum ofapproximately 1 mtorr at 600° C. for 10 min. A highly reflective smoothadherent coating of metallic Os formed on the substrate. This exampleshows that Os(hfb)(CO)₄ is an effective CVD precursor forosmium-containing films, that standard CVD equipment may be used, andthat carrier gases and high temperatures are not required.

EXAMPLE 8

Deposition from Os(hfb)(CO)₄ was carried out as in Example 7 and theresulting osmium films analyzed by XRD, SEM, stylus profilometry, andresistivity measurements. XRD showed the films to have a hexagonalstructure and are polycrystalline with no preferred orientation. AESshowed, after Ar⁺ sputtering, that the carbon and oxygen content in thefilms is 30% and 1%, respectively. Fluorine could not be observed by AESin these films. The resistivity of the films was measured by a standardfour-point probe method and gave a value of 750 μΩ/cm; the value for theresistivity of bulk osmium is 8.1 μΩ/cm. Stylus profilometry on asubstrate which had a portion of its surface masked, showed a filmthickness of 1500Å for a ten-minute deposition at 600° C. which yields adeposition rate of 15 nm/min. This example shows that the Os(hfb)(CO)₄CVD precursor gives osmium films at high deposition rates. The carboncontent can be lowered using hydrogen as the carrier gas.

EXAMPLE 9

Ru(hfb)(CO)₄ (0.797 g) was passed through the reactor system describedin Example 2 at 150° C. for 30 min under a dynamic vacuum ofapproximately 1 mtorr. A yellow crystalline solid (0.53 g) deposited onthe cooler portions of the reactor system. Spectroscopic analysis of theyellow crystalline solid showed it to be the binuclear complex Ru₂ [C₄(CF₃)₄ ](CO)₆. A 72% yield of the product was obtained in this flashvacuum pyrolysis. Spectroscopic data for Ru₂ [C₄ (CF₃)₄ ](CO)₆ : IR(cm⁻¹, pentane) 2117 (m), 2096 (s), 2064 (s), 2054 (s), 2037 (s), 2021(w); ¹⁹ F NMR (ppm from CFCl:, CD₂ Cl₂) -45.2 (br s, 6F), -51.1 (br s,6F); ¹³ C NMR (ppm, CD₂ Cl₂) 121.6 (q, J_(C-F) =280.8 Hz), 126.5 (q,J_(C-F) =274.6 Hz), 138.8 (s), 139.3 (s), 189.9-190.5 (br); Anal.Calcd.: C, 24.22; H, 0.00; Found: C, 24.23; H, 0.05; EI-Mass Spectrum:m/e =696 for parent ion Ru₂ C₁₄ O₆ F₁₂ ⁺ followed by fragmentscorresponding to loss of 6 CO ligands; m.p. 139°-140° C. This exampleshows that Ru(hfb)(CO)₄ thermally reacts in the gas phase to yield anovel product, Ru₂ [C₄ (CF₃)₄ (CO)₆, which is an air stable, easilyhandled material.

EXAMPLE 10

Ten mg of Ru(hfb)(CO)₄ and 5 ml of dry toluene were placed in a 50 mlpyrex thick-wall tube and the mixture was stirred and heated to refluxunder nitrogen. The reaction solution became yellow within 10 min. Afterheating and stirring for 3 hrs, the reaction mixture was cooled to roomtemperature and the solvent was removed under vacuum. A yellow solid wasobtained as the only product and it was shown to be identical to the Ru₂[C₄ (CF₃)₋₄ ](CO)₆ prepared in Example 9. This example shows the novelproduct Ru₂ [C₄ (CF₃)₄ ](CO)₆ may be prepared by conventional solutiontechniques in good yield.

EXAMPLE 11

Os(hfb)(CO)₄ was passed through the reactor system described in Example2 at 300° C. for 10 min under a dynamic vacuum of approximately 1 mtorr.In addition to a thin metallic Os coating on the reactor tube, a whitecrystalline solid deposited on the cooler portions of the reactorsystem. Spectroscopic analysis of the solid showed it to be thebinuclear complex Os₂ [C₄ (CF₃)₄ ](CO)₆. Spectroscopic data for Os₂ [C₄(CF₃)₄ (CO)₆ : IR (cm⁻¹, CH₂ Cl₂) 2120 (m), 2093 (s), 2057 (m), 2035(m), 2012 (m); ¹⁹ F NMR (ppm from CFCl₃, CD₂ Cl₂) -45.7 (br s, 6F),-50.8 (br s, 6F); EI-Mass Spectrum: m/e =788 for parent ion Os₂ C₁₄ O₆F₁₂ ⁺ - 3CO's, 704 for parent ion - 6CO' s. The example shows thatOs(hfb)(CO)₄ thermally reacts in the gas phase to yield a novel product,OS₄ [C₄ (CF₃)₄ ](CO)₄, which is air stable, easily handled material.

EXAMPLE 12A

Ru₂ [C₄ (CF₃)₄ ](CO)₆ (38.5 mg) in a quartz boat was placed in thecenter of the reactor tube described in Example 2. The siliconsubstrates were placed towards the exit of the reactor tube. Theprecursor was pyrolyzed at 600° C. for 10 min to give highly reflectivesmooth adherent coatings of metallic Ru on the substrates. AES, asdescribed in Example 5, gave oxygen and fluorine contents in the filmsof 1% and 0.9%, respectively. The carbon content, as determined by theI₂₇₃ /I₂₃₁ intensity ratio, is below the detection limit. This exampleshows the novel Ru₂ [C₄ (CF₃)₋₄ ](CO)₆ complex is an effective CVDprecursor for ruthenium containing films, that standard CVD equipmentmay be used, that the films obtained are of high quality, and thatcarrier gases and high temperatures are not required.

EXAMPLE 12B

Using the reactor system described in Example 2,

ruthenium thin films were deposited from Ru₂ [C₄ (CF₃)₄ ](CO)₆ onSi<100> substrates. The deposition was performed without a carrier gasunder a dynamic vacuum of 1 to 10 mtorr at 500° C. for 30 min. Theprecursor and inlet system

are warmed to about 60°-70° C. with electric heating tape to assist inprecursor volatilization. A highly reflective, smooth, adherent coatingof metallic Ru formed on the substrates. The film contains no oxygen,fluorine, or carbon by AES. Stylus profilometry showed the depositionrate to be 20 A/min. The resistivity of the film is 440 μΩ/cm asmeasured by a standard four-point probe method. This example shows thatRu₂ [C₄ (CF₃)₄ ](CO)₆ is an effective CVD precursor for high qualityruthenium containing films, that standard precursor inlet systems andstandard CVD equipment may be used, and that carrier gases and hightemperatures are not required.

EXAMPLE 13

A 100 watt mercury lamp fitted with a UV transmitting light guide(Ultracure 100SS, Efos, Inc., Mississauga, Ontario, Canada) wasincorporated into the reactor system described in Example 2, so that thelight guide illuminated the quartz reactor tube inside the furnaceentrance. The furnace is heated to 150° C. and evacuated toapproximately 1 mtorr for 30 minutes. The reactor was isolated from thevacuum pump and backfilled with a partial pressure of Ru₂ [C₄ (CF₃)₄](CO)₆. The reactor tube was held at 150° C. and irradiated with theunfiltered output of the lamp for 10 min under a static vacuum. A thinmetallic Ru coating was observed on the reactor tube walls in the areailluminated by the lamp. This example shows that the CVD of rutheniumfilms from the novel Ru₂ [C₄ (CF₃)₄ ](CO)₆ precursor can bephotolytically decomposed and that the depositions can be performedunder static vacuum.

EXAMPLE 14

The CVD reactor of Example 2 was fitted with a U-tube mercury manometerdirectly downstream of the reactor furnace and upstream of the vacuumtraps. The system was loaded with Si wafers as in Example 2, evacuatedto 10 mtorr, and the reactor was heated to 500° C. for 30 min. Air waspassed over the Ru(hfb)(CO)₄ precursor at 25° C. and through the reactorat a 128 cc/min flow rate for 10 min which provided a pressure of 35torr in the reactor. The air flow was stopped, the reactor cooled, andthe Si wafers removed. The wafers contain a dark metallic adherent filmof ruthenium oxide which show a uniform concentration of oxygenthroughout the depth of the film by AES. The fluorine concentration isbelow the AES detection limit. This example shows that the depositionsmay be carried out with a carrier gas, the carrier gas may be a reactivegas, the reactive gas may be air, and that ruthenium oxide films may beformed.

EXAMPLE 15

The CVD reactor of Example 2 was fitted with a U-tube mercury manometerdirectly downstream of the reactor furnace and upstream of the vacuumtraps. The system was loaded with Si wafers as in Example 2, evacuatedto 10 mtorr, and the reactor heated to 500° C. for 30 min. Oxygen waspassed over the Ru(hfb)(CO)₄ precursor at 25° C. and through the reactorat a 128 cc/min flow rate for 15 min which provides a pressure of 115torr in the reactor. The oxygen flow was stopped, the reactor cooled,and the Si wafers removed. The wafers contain a dark metallic adherentfilm of ruthenium oxide which shows a uniform concentration of oxygenthroughout the depth of the film by AES. Trace amounts of fluorine arealso detected by AES. This example shows that the depositions may becarried out with a carrier gas, the carrier gas may be a reactive gas,the reactive gas may be oxygen, and ruthenium oxide films may be formed.

EXAMPLE 16

The CVD reactor of Example 2 was fitted with a U-tube mercury manometerdirectly downstream of the reactor furnace and upstream of the vacuumtraps. The system was loaded with Si wafers as in Example 2, evacuatedto 10 mtorr, and the reactor was heated to 550° C. for 30 min. Hydrogenwas passed over the Os(hfb)(CO)₄ precursor at 25° C. and through thereactor at a 243 cc/min flow rate for 3.5 min which provided a pressureof 34 torr in the reactor. The hydrogen flow was stopped, the reactorcooled, and the Si wafers removed. The wafers contain a metallicadherent film which contains 86% Os, 10% C, and 4% 0 by AES. The film ispolycrystalline by XRD. This example shows that the depositions may becarried out with hydrogen, and the carbon levels in the group VIII metalfilms may be lowered by using a reducing carrier gas.

EXAMPLE 17

Using the reactor system described in Example 2, iron thin films weredeposited on Si<100> wafers from (CO)₄ Fe[N(CH₃)₃ ]. The precursor wasprepared as disclosed by J. Elzinga et al., J. Org. Chem., 45, 3957(1980). The deposition was performed without a carrier gas under adynamic vacuum of 1 to 10 mtorr at 300° C. for 20 min. A highlyreflective, smooth, adherent coating of metallic Fe was formed on thesubstrate. The film was shown to contain 85.3% Fe, 8.4% 0, and 6.3% C byAES; no nitrogen was detected. Another film was deposited from (CO)₄Fe[N(CH₃)₃ ] under identical conditions except that the depositiontemperature was 150° C. and the deposition time was 40 min. A metallicFe film was formed on the substrate and the film shown to contain 78.7%Fe, 15.8% 0, 4.8% C, and 0.7% N by AES. This example shows that (CO)₄Fe[N(CH₃)₃ ] is an effective CVD precursor for iron containing films,that standard CVD equipment may be used, that carrier gases and hightemperatures are not required, and that film composition may becontrolled by deposition temperature.

EXAMPLE 18

Using the reactor system described in Example 2, iron thin films weredeposited on Si<100> wafers from (CO)₄ Fe[P(OCH₃)₃ ]. This precursor wasprepared as disclosed by S.B. Butts et al., J. Organomet. Chem. 169, 191(1979). The deposition was performed without a carrier gas under adynamic vacuum of 1 to 10 mtorr at 500° C. for 30 min. The precursor andinlet system were warmed to about 65° C. with electric heating tape toassist in precursor volatilization. A highly reflective, smooth,adherent coating of metallic Fe formed on the substrates. The filmcontains 56.1% Fe, 13.6% 0, 6.9% C, and 23.4% P by AES. This exampleshows that (CO)₄ Fe[P(OCH₃)₃ ] is an effective CVD precursor for ironcontaining films, that standard CVD equipment may be used, that carriergases and high temperatures are not required, and that film compositionmay be controlled by controlling the chemical structure of theprecursor.

EXAMPLE 19

Using the reactor system described in Example 2, iron thin films weredeposited on Si<100> substrates from Fe₂ (C₄ H₄)(CO)₆ (prepared from Fe₃(CO)₁₂ and thiophene according to G. Dettlaf et al., J. Organomet.Chem., 108, 213 (1976)). The deposition was performed without a carriergas under a dynamic vacuum of 1 to 10 mtorr at 500° C. for 30 min. Theprecursor and inlet system were warmed to about 65° C. with electricheating tape to assist in precursor volatilization. A highly reflective,smooth, adherent coating of metallic Fe formed on the substrates. Thefilm contains 62.1% Fe, 3.4% 0, and 34.0% C, by AES. A trace amount ofsulfur (0.5%) was also detected which may result from residual thiophenecontaminant in the precursor. This example shows that Fe₂ (C₄ H₄)(CO)₆is an effective CVD precursor for iron containing films, that standardCVD equipment may be used, and that carrier gases and high temperaturesare not required.

All publications and patents are herein incorporated by reference to thesame extent as if each individual publication or patent was specificallyand individually indicated to be incorporated by reference.

It will be apparent to one of ordinary skill in the art that manychanges and modifications can be made in the invention without departingfrom the spirit or scope of the appended claims.

What is claimed is:
 1. A method for applying a metal film on the surfaceof a substrate comprising employing the techniques of chemical vapordeposition to decompose a vapor comprising a compound of the formula:##STR2## wherein (a) each M is Fe, Ru or Os; and(b) each R is H, OH,halo, (C₁ -C₁₀)alkyl, (C₁ -C₁₀)perfluoroalkyl, (C₆ -C₁₀)aryl or two Rtaken together are benzo;so as to deposit a film comprising Fe, Ru, Osor mixtures thereof on said surface.
 2. The method of claim 1 whereinboth M are Fe, Ru or Os.
 3. The method of claim 2 wherein both M are Ruor Os.
 4. The method of claims 2 or 3 wherein R is H, OH, halo, (C₁-C₆)alkyl, (C₁ -C₆)perfluoroalkyl and phenyl.
 5. The method of claim 4wherein R is H, trifluoromethyl, phenyl or methyl.
 6. The method ofclaim 1 wherein the deposition is carried out at about 150°-700° C. 7.The method of claim 6 wherein the deposition is carried out at about300°-600° C.
 8. The method of claim 1 wherein the deposition is carriedout under a vacuum of about 1-100 mtorr.
 9. The method of claim 1wherein the decomposition of the vapor is induced thermally,photolytically or both thermally and photolytically.
 10. The method ofclaim 1 further comprising employing a carrier gas to transport thevapor to the surface of the substrate.
 11. The method of claim 1 whereinthe film consists essentially of Ru, Os or Fe.
 12. The method of claim11 wherein the film consists essentially of Ru or Os.
 13. The method ofclaim 1 wherein the vapor further comprises an amount of an oxidizingagent effective to deposit a film of ruthenium oxide, osmium oxide oriron oxide on said surface.
 14. The method of claim 13 wherein theoxidizing agent is provided by CO₂, N₂ O, tetrahydrofuran, oxygen, airor steam.
 15. The method of claim 13 wherein the oxidizing agent ismixed with a carrier gas.
 16. The method of claim 1 wherein a coherentconformal film comprising Ru, Os or Fe is deposited on a substrate ofirregular topography.
 17. The method of claim 1 wherein the filmconsists essentially of Ru, Os or Fe.